Water-soluble, unsymmetrical chromium-containing azo dyestuffs



United States Patent Office 3,391,132 Patented July 2, 1958 ABSTRACT OFTHE DISCLOSURE Water soluble unsymmetrical 1:2 chromium complex dyes ofthe formula 2 1 1 0 \cr/ 0 u R'----Z2 I) N N l J.

linked in u-position to the -CH= and in the ,B-position to the adjacentoxygen bridge,

R represents hydrogen, lower alkyl, hydroxy-lower alkyl 'or phenyl, oneof X and X; represents the grouping G-N=N and the other X representsGN=N-- or hydrogen, nitro, halogen, phenylsulfonyl or loweralkanoylamino;

G represents phenyl, halogen-substituted phenyl, lower alkyl-substitutedphenyl, nitrophenyl, lower alkoxyphenyl, phenoxyphenyl, lower alkylphenoxyphenyl, halogen-substituted phenoxyphenyl, phenyl-sulfonylphenyl,lower alkyl-substituted phenyl-sulfonyl-phenyl or halogen-substitutedphenyl-sulfonyl-phenyl, naphthyl, 2-benzothiazolyl, Z-thiazolyl,2-imidazolyl, 2-benzimidazolyl or pyridyl;

Y represents hydrogen, nitro, halogen or lower alkyl;

Y represents hydrogen or halogen;

Z represents sulfo, carboxyl, sulfamyl, lower alkyl-sulfonyl, or N-Ioweralkyl-substituted sulfamyl; and

Z represents hydrogen or sulfarnyl, lower alkylsulfamyl or N-loweralkyl-substituted sulfamyl;

each of Z and Z being linked to an aromatic ring carbon atom of A, B, C,D, E, or G, which new dyestuffs are suitable for the dyeing and printingof fibers containing polyamide, e.g. natural polyamide material,especially wool or silk or leather, or synthetic polyamide material suchas nylon or polyurethane fibers.

This invention relates to new water soluble, chromiumcontainingdyestuffs, a process for the production thereof, their use for thedyeing of fibers containing polyamide as well as, as industrialproducts, fibrous polyamide materials dyed with these dyestulfs.

The novel dyestuffs to which the invention relates are unsymmetricalchromium complexes, of a molar chrornium-to-dyestuif ratio of 1:2, inwhich one of the dyestuli radicals of the complex molecule is ano,o'-dihydroxy azomethine dyestuif radical and the other is ano-hydroxyo-amino-monoazo dyestuff radical, which dyestutfs aredistinguished from known mixed chromium complex dyes by the o'-aminobridge on the one hand and by an arylazo substituent in one or bothmoieties of the aforesaid azomethine dyestuii radical, on the otherhand.

These dyestuffs possess the unexpected property of dyeing polyamidefibers such as wool, silk or nylon level with a combination of excellentfastness to wet media, especially to washing, and alight fastness whichis surprisingly superior to that of structurally closest known dyes.

More in particular, the invention concerns the novel, water-solubledyestuffs of the formula wherein D represents phenyl or L2 linked ine-position to the -CH=, and in p-position to the adjacent oxygen bridge,

II if R represents hydrogen, lower alkyl, hydroxy-lower alkyl or phenyl,one of X and X represents the grouping 'N=N- and the other X representsGN=N or hydrogen, nitro, halogen, phenylsulfonyl or lower alkanoylamino;

G represents phenyl, halogen-substituted phenyl, lower alkyl-substitutedphenyl, nitrophenyl, lower alkoxyphenyl, phenoxyphenyl, loweralkylphenoxyphenyl, halogen-substituted phenoxyphenyl,phenyl-sulfonylphenyl, lower alkyl-substituted phenyl-sulfonyl-phenyl orhalogen-substituted phenyl-sulfonyl-phenyl, naphthyl, 2-benzothiazo1yl,2-thiazolyl, Z-imidazolyl, 2-benzimidazolyl or pyridyl;

Y; represents hydrogen, nitro, halogen or lower alkyl;

Y represents hydrogen or halogen;

Z represents sulfo, carboxyl, sulfamyl, lower alkylsulfonyl, or N-loweralkyl-substituted sulfamyl; and

Z represents hydrogen or sulfamyl, lower alkylsulfamyl or N-loweralkyl-substituted sulfamyl,

each of Z and Z being linked to an aromatic ring carbon atom of A, B, C,D, E or G, which new dyestuffs are suitable for the dyeing and printingof fibers containing polyamide, e.g. natural polyamide material,especially wool or silk or leather, or synthetic polyamide material suchas nylon or polyurethane fibers.

The dyeings on polyamide fibers attained with the dyestufis according tothe invention have very good fastness to light, to alkali, to rubbingand good wet fastnesses, in particular good washing, milling and seawater fastness.

Polyamide dyeings, and epsecially wool dyeings obtained with thedyestuffs according to the invention unexpectedly have fastness t-omilling and to washing under severe conditions (of degree 3) which issuperior to that of known chromium-containing dyestuffs which contain nogroups which dissociate acid in water and which contain 1 molecule of ano-hydroXy-o'-amino-monoazo dyestuff and 1 molecule of ano,o'-dihyd-roxyazomethine dyestulf having no arylazo groups, perchromium atom. Compared with known dyestuffs of the same type whichcontain sulfonic acid groups, the new dyestuffs show superior fastnessto washing (even of degree 3) of their wool dyeings, a greaterpropensity for the level dyeing of heterogeneous mixtures of wool ofvarious origin (tippy wool) and also better fastness to washing and hotwater (for instance with regard to the change in shade of their dyeingson silk). Compared with other known chromium complex dyestuffs lackingan aforesaid arylazo-substituent, they have better fastness to washingof degree 3 and to milling, greater stability against injury by boilingand increased drawing power from a neutral bath as well as less tendencyto give tippy dyeings on wool. Compared with known water-soluble,chromium-containing dyestuffs which contain per chromium atom 1 moleculeof an o,o'-dihydroxymonoazo dyestuff and 1 molecule of ano,o'-dihydroxyazo-azomethine dyestuff, the wool dyeings of the dyestuffsaccording to the invention have surprisingly better light fastness,particularly with light shades.

(power alkyl) 4 Among the dyestuffs of Formula IA, those falling underthe following formula:

wherein each of X X and R has the same meaning as in Formula IA, Yrepresents hydrogen or nitro, and Z represents -SO H or COOH linked toone of the aromatic ring carbon atoms of benzene nucleus A ornaphthalene nucleus E", impart particularly good light and wet fastnessproperties to dyeings thereof on polyamide fibers, and especially onwool. Optimal light fastness in wool dyeings is afforded by dyestuffs ofFormula IB in which R is hydrogen and Z is an SO H group linked to acarbon atom of naphthalene nucleus E".

Water-soluble, chromium-containing dyestuffs are obtained by reactingeither simultaneously or one after the other, a monoazo dyestuff of theformula OH III-R ii-N=N-E (I) and an azo-azomethine dyestuff of theformula [BN=CH]|)l{N=N-G) in Ho i 11 the dyestuffs of Formulas I and IItogether containing at least one water-solubilizing group, with an agentgiving off chromium to form a complex dyestuff of the formula whichcomprises the dyestuffs of Formula IA.

In these Formulas I, II and III,

A, B, and D each represent a radical of the benzene or naphthaleneseries which contains O in a position adjacent to the azo or azomethinebond,

E represents a radical of the naphthalene or pyrazole series whichcontains I IR in a position adjacent to the azo bond, R representshydrogen or an unsubstituted or substituted lower alkyl or aryl radical,G represents a carbocyclic-aromatic or heterocyclicaromatic radical, Wrepresents a water-solubilizing group, and m and n each represent 1 or2.

If E is a naphthalene radical then it is advantageously bound in the1,2-position to the azo and amino group.

If E -is a pyrazole radical then it is bound in the 4-position to theazo group and in S-pesition to the amino group. This pyrazole radical ispreferably substituted in the l-position by an aromatic radical,particularly one of the benzone series, and in the 3-position by analiphatic radical, i.e. a lower alkyl radical.

If R is an unsubstituted lower alkyl radical then it is, for example,the methyl or ethyl radical. If this radical contains substitutents,then examples thereof are the hydroxyl group, lower alkoxy groups suchas the methoxy or ethoxy group, or the cyano group. If R is an arylradical then it is chiefly one of the benzene series.

If G is a carbocyclic-aromatic radical then it is particularly a radicalof the benzene or naphthalene series. However, if G is aheter-ocyclic-aromatic radical, then it is, for example, the radical ofa S-membered heterocycle such as a Z-thiazolyl, Z-benzthiazolyl,2-imidazolyl or Z-benzimidazolyl radical, or the radical of a G-memberedheterocycle such as a pyridyl radical.

W represents both a group which dissociates acid in Water such as thesulfonic acid or carboxyl group, as well as a group which does notdissociate acid in water, e.g. the sulfonic acid amide, sulfonicacid-N-methylamide, methylsulfonyl or ethylsulfonyl group. Preferably Wis the sulfonic acid group and n is 1. However, if W represents a groupwhich does not dissociate acid in water, then n is 2. -N=NG can be boundboth to B as well as to D. If there are two such groups (i.e. m==2),then preferably one is bound to B and the other to D. In the lattercase, the radicals G can be identical or different.

The carbocyclic-aromatic radicals is the compounds of Formulas I, II andIII can contain the substituents usual in dyestuffs, for example,nucleophilic substituents such as hydrocarbon groups, particularly loweralkyl groups, ether groups, advantageously lower alkoxy and aryloxygroups, or acylamino groups, e.g. alkanoylamino or aroylamino groups, orelectrophilic substituents such as halogens, e.g. fluorine, chlorine orbromine, non-water solubilizing carboxylic acid amide and sulfonic acidamide groups substituted at the introgen atom, in the case of sulfonicacid amide groups, e.g. sulfonic acid-Narylamide or sulfonicacid-Nalkyl-N-arylamide groups, also carboxylic acid ester or sulfonicacid aryl ester groups, the nitro, cyano or trifiuoromethyl group oracyl groups such as lower alkanoyl, aroyl groups, or alkylsulfonylgroups having at least 3 carbon atoms, or arylsulfonyl groups; inaddition G can also contain arylazo groups of the carbocyclic orheterocyclic series.

Most of the starting materials of Formula I are known, or they can beproduced by known processes, e.g. by coupling the diazonium compound ofan optionally Oalkylated or O-acylated o-aminophenol or o-aminonaphtholof the formula with a naphthylamine of the formula HE--NHR which couplesin a position adjacent to the amino group, and subsequently convertingany alkoxy or acyloxy group present into the hydroxyl group.

The starting materials of Formula II are obtained, for example, bycondensation of an o-hydroxyarylamine of the formula with ano-hydroxyaryl aldehyde of the formula O=CH-D--OH at least one of thecomponents containing the group --N=NG. This group can be introduced inthe known way into the-optionally N acylated-o-hydroxya'rylamine or theo-hydroxyaryl aldehyde by coupling it with a diazonium compound G-Nf.The condensation of the amine with the aldehyde to form theazo-azomethine of Formula II is performed (optionally aftersaponification of the N-acylated o-hydroxyarylamine) in water or in anorganic solvent such as a lower alkanol, an alkylene glycol monoalkylether or the amide of a lower fatty acid and, advantageously, in aneutral or weakly akaline medium. The azo-azomethine dyestuif of FormulaII can, in many cases, be used directly without having to be isolatedfor the production of the dyestuffs of Formula III according to theinvention.

The simple salts of trivalent chromium, for example, are used as agentsgiving off chromium such as chromic fluoride, chromic acetate, chromicformate or chromic sulfate or potassium or ammonium chromic sulfate,optionally in the presence of those compounds which, with the chromicsalts, canform complex compounds which are soluble in an alkalinemedium. Examples of such compounds are tartaric acid, citric acid,lactic acid or salicylic acid. Also however, complex chrornic salts canbe used, for example, those obtained by reaction of simple chromiumsalts with compounds capable of complex formation.

The reaction of the agents giving off chromium with the monoazo andazo-azomethine compounds as defined of Formulas I and II is performed,for example, in aque ous slurry, in aqueous solution or in the melt, eg,in the melt of the alkali metal salt of a lower fatty acid, or in anorganic solvent and, optionally, in the presence of acid binding agentssuch as sodium or potassium acetate or carbonate. Examples of suitablesolvents are amides of lower fatty acids such as formamide or dimethylformamide, or alcohols such as alkanols or alkylene glycols and theirlower monoalkyl ethers.

If the monoazo and azo-azomethine dyestuffs as defined are both reactedtogether with the agents giving off chromium, these dyestuffs are usedin about equimolecular proportions.

However, it is advantageous to perform the reaction with the agentsgiving off chromium in steps. Thus, preferably a monoazo dyestuff ofFormula I is first reacted with an agent giving off chromium to form acomplex chromium compound which contains 1 molecule of a monoazodyestuff of Formula I bound! in complex linkage to 1 chromium atom. Thisis done, advantageously, at temperatures from -140 C., open or underpressure, particularly in water or in an organic solvent such as analcohol, and in an acid medium. Then the complex 1:1 chromium compoundis reacted with an azo-azomethine dyestuff as defined of Formula II toform the complex chromium compound of Formula III. In many cases, thecomponents, i.e. the corresponding amines and aldehydes, can also beused instead of this azo-azomethine dyestuff.

This operation is advantageously performed in aqueous or organic mediumand, with advantage, is the presence of acid binding agents such assodium or potassium acetate or carbonate or dilute sodium or potassiumhydroxide solution.

The following non-limitative examples illustrate the invention. Thetemperatures are given therein in degrees centigrade. Percentages aregiven by weight.

Example 1 H I 3 cu H NO 0 O I 0 R or 36.2 g. of the azo-azornethinedyestuff obtained by condensation of1-hydroxy-2-formyl-4-phenylazobenzene with 71-hydroxy-2-amino-4-nitrobenzene are added at about 85 to a solution of40 g. of anhydrous sodium carbonate in 1000 ml. of water. 48.3 g. of the1:1 chromium complex compound, corresponding to 5.2 g. of chromium and43.3 g. of the monoazo dyestuif: 1-hydroxy-2-amino-4,6-dinitrobenzene-1-aminonaphthalene-4-sulphonic acid are added to this solution. Thesuspension obtained is heated for 1 /2 hours at 8595 whereupon an olivegreen solution is obtained. The dyestuflf formed is salted out withsodium chloride, filtered off and dried. The dyestufl. obtained,corresponding to the above formula, is a dark powder which dyes wool inolive green shades.

Example 2 5:! 08.1 o (X X) l N0 I01 27.6 g. of1-hydroxy-2-formyl-4-[naphthyl(1)-azo]- benzene are suspended in asolution of 40 g. of anhydrous sodium carbonate in 2000 ml. of water atabout 85 and 15.4 g. of 1-hydroxy-2-amino-4-nitrobenzene and 48.3 g. ofthe 1:1 chromium complex compound corresponding to 5.2 g. of chromiumand 43.3 g. of the monoazo dyestufi': 1 hydroxy 2 amino 4,6dinitrobenzene- 1- aminonaphthalene-4-sulphonic acid are added. Thesuspension obtained is heated for 1 /2 hours at 85-95". The dyestufiformed is then salted out, filtered off and dried. It corresponds to theabove formula and is a dark powder which dyes polyamide fibres,particularly wool, in olive green shades having good fastnessproperties.

Example 3 42.1 g. of the azo-azomethine dyestufi obtained bycondensation of 1-hydroxy-2-formyl-4-phenylazobenzene with1-hydroxy-2-amino-4-phenylazobenzene are suspended in a solution of 40g. of anhydrous sodium carbonate in 1000 ml. of water at about 85. 48.3g. of the 1:1 chromium complex compound corresponding to 5.2 g. ofchromium and 43.3 g. of the monoazo dyestuff: 1-hydroxy-2-amino-4,6-dinitrobenzene 1 aminonaphthalene 4 sulphonic acid are addedto this suspension. The reaction mixture is heated for 1 hours at 85-95and after this time the dyestufi is precipitated by the addition ofsodium chloride. It is a dark powder which dyes wool from a neutral toweakly acid bath in brown-olive shades having good fastness properties.

8 Example 4 3 At about 41.2 g. of the azo-azomethine dyestuff obtainedby condensation of 1-hydroxy-2-formyl-4-[naphthyl(1')-azo]-benzene with1-hydroxy-2-amino-4-nitrobenzene are suspended in the solution of 1000ml. of H 0 and 25 .g. of solid NaOH. 43.8 g. of the 1:1 chromium complexcompound corresponding to 5.2 g. of chromium and 38.8 g. of the monoazodyestuff: l-hydroxy-Z-amino- 5-nitrobenzene 2-aminonaphthalene-6-sulphonic acid are added. The mixture is heated for 1 /2hours at 85- whereupon an olive green solution is formed. The dyestuffformed is salted out with sodium chloride, filtered off and dried. It isa dark powder which dyes wool from a neutral to weakly acid bath inolive green shades having good fastness properties.

Example 5 42.1 g. of the azo-azomethine dyestuif obtained bycondensation of 1-hydroxy-2-formyl-4-phenylazobenzene and1-hydroxy-2-amino-4-phenylazobenzene are dissolved in a mixture of 600ml. of water, 600 ml. of ethylene glycol monomethyl ether and 40 g. ofanhydrous sodium carbonate at 85. 43.8 g. of the 1:1 chromium complexcompound corresponding to 5.2 g. of chromium and 38.8 g. of the monoazodyestufl:1-hydroxy-2-amino-S-nitrobenzeneZ-amino-naphthalene-6-sulphonic acid areadded to this solution. The mixture is heated for 1 /2 hours at 85-95"whereupon a dark green dyestuff solution is formed. The dyestufl issalted out by the addition of sodium chloride, filtered 01f and dried.It is a dark powder which dyes wool from a neutral to weakly acid bathin brownish olive shades having gOOd fastness properties.

Example 6 Q a 0 0 N0 C CH 2 H ll 45.7 g. of the azo-azomethine dyestuifobtained by condensation of 1-hydroxy-2-formyl-4-phenylazobenzene with1-hydroxy-2-amino-4-phenylsulphonylbenzene are dried. It is a darkpowder which dyes wool from a neutral to weakly acid bath in olive greenshades having good fastness properties.

suspended in a solution of 40 g. of anhydrous sodium Example 8 carbonatein 1000 ml. of water at about 85. Also 49.7 g. 5 o of the 1:1 chromiumcomplex compound corresponding to 5.2 g. of chromium and 44.7 g. of themonoazo dyeca n stuff: 1-hydroxy-2-amino-4,6-dinitrobenzene Z-methylgaminonaphthalene-7-sulphonic acid are added. The mix- 0 ture obtained isheated for 1 /2 hours at 85-95 where- 10 o upon an olive green solutionis formed. The dyestufi I formed is salted outwith sodium chloride,filtered off and l dried. The dyestufl obtained corresponds to the above0 m formula. It is a dark powder which dyes wool from a Q So a neutralto weakly acid bath in yellowish olive shades hav- 3 ing good fastnessproperties. n 3

Example 7 45.4 g. of the azo-azomethine dyestuff obtained bycondensation of 1-hydroxy-2-formyl'4-(4'-phenoxyphenylazo)-benzene with1-hydr0Xy-'2-amin0-4-nitr0benzene are H i I on it dissolved in a mixtureof 1000 ml. of water, 500 ml. of 0 2 ethylene glycol monomethyl etherand 40 g. of anhydrous sodium carbonate at about 85 43.8 g. of the 1:1chro- 0 0 'mium complex compound corresponding to 5.2 g. of chromium and38.8 g. of the monoazo dyestuif: l-hyl droxy 2 amino 5 nitrobenzene- 2amino naphc H 0 1m thalene-S-sulphonic acid are then added. Thesuspension 5 H obtained is heated for 1 /2 hours at 85-95 whereupon anolive green solution is formed. The dyestutf is then salted 2" H a H 5out with sodium chloride, filtered off and dried. It is a dark powderwhich dyes wool from a neutral to weakly 52.4 g. of the azo-azomethinedyestutf obtained by acid bath in olive shades having good fastnessproperties. condensation of 1-hydroxy-2.-formy1-4-[2-(4-amyl-phe- If,instead of the azo-azomethine dyestuff mentionednoxy)-phenylazo]-benzene with 1-hydroxy-2-amino-4- above, one of thosegiven in "column II of the following nitrobenzene are dissolved in amixture of 1000 ml. of table is used and, if instead of the 1:1 chromiumcomwater, 500 ml. of ethylene glycol monomethyl ether and plex compoundgiven, a 1:1 chromium complex comg. of anhydrous sodium carbonate atabout pound of one of the azo dyestuffs given in column III 48.3 g. ofthe 1:1 chromium complex compound correof the same table is used andotherwise the same procesponding to 5.2 g. of chromium and 43.3 g. ofthe mon0 dure as given in Example 8 is followed, then correspondazodyestuff: 1-hydroxy-2-amino-4,6-dinitrobenzene 1- 40 ing 2:1 chromiumcomplex compounds are obtained aminonaphthalene-4-sulphonic acid arethen added. The which have the shades given in column IV of this table.suspension so obtained is heated for 1 /2 hours at 85-95 Theazo-azomethine dyestuffs given in the table are prowhereupon an olivegreen solution is formed. The dyeduced by condensing the correspondingaldehydes with stufl is salted out with sodium chloride, filtered 0E andthe aminophenols.

TABLE I II III IV Shade of the No. Azo-azomethine dyestuti Azo dyestufl2:1 Chromium complex compound on wool 9 NH, Greenlsh olive.

NO: I Q A -0I-I N=N -CH=N soQ 01N- -NH1 10 Same as No. 9 Gre n.

OzN OH NH]: @NHZ 1103803 11 ..do N Oz Brownish olive.

OH NH:

O2N' NH! J 'flABLE continued I II III IV Shade of the No. Azo-azomethlnedyestufi Azo dyestufi 2:1 Chromium complex compound on wool 12 Same asNo. 9 NO, 17H Olive.

OgN NH:

13 ..do Green.

0;N O H NH:

14 do I? O Olive.

-0 H H O a S N H:

07N N Hg 15 ..do Do.

-0 H H 0 s N H] 0 EN N H,

16 N0: Brownish olive.

O H HO 0 H NH; N=N CH=N N 0, g OzN N Ha 17 Same as No. 16 .3 1T0: D0.

-OH NH:

HO,S N H:

18 do Yellowish green.

OQN O H N H:

I SO;H

19 d0 IIIO O H H0 8 N Hz Brownish olive.

O N N H2 20. do Do.

0 H H O a S- N H:

OzN- N H:

21 Green.

OH HO OaN 0H NH;

H0 8 N=N CH: NO, NH;

22 NH: Brown.

011 HO O H N=N- -'N=CH OgN- -NH;

SO H

TABLE-Contlnued I II III IV Shade of the N0. Azo-azomethine dyestuff Azodyestufi 2:1 Chromium complex compound on W001 170; IIQHQ 23 O 0 H H O OH Yellowish olive.

N=N CH=N NO; OQN N H;

24 Same as No. 23 02H OH. NH: Green.

NH; H0 8- 25 .do -0 H NH; Yellowish olive,

O H- --NH;

I SO :H

26 .do 0H H035 NH-CH3 Brownish olive.

OzN- NH! IYIO a N O IYIH:

27 O H HO 0 H Olive.

N: N 20H N 01 O :N N Hg N O 2 IIIHQ 28 -OH HO N 0, 0H Brownlsh olive.

N ==N- CH: 0 gN- NH:

29 OH HO OaN -0H NH Green.

N=N C H=N -N=N N H,

| laHu S 0 3H 30 H OH HO OzN OH NH: Do.

-N=N- CH=N N 0: N H2 1 C15Hu- S0311 If 01 IYHI 31 O 0 H HO OH Olive.

N=N N=CH- OaN- NH:

N O 3 NH:

32 C1 OH HO O H D0.

-N=N -N= OH N 0 OgN NH;

TABLECon'tinued I II III IV Shade of the No. Azo-azomethine dyestufi Azodyestufl 2:1 Chromium complex compound on wool 33 OH HO OH N H: Olive).

N: CH=N NO3 OzN NH N 0 N H:

34 01 -OH HO OH Green.

N=N- CH=N Cl O N NH;

35 Br- OH HO Same as NO. 34 Do.

-N=N CH=N CE:

36 H5020 OH-H ...d0 Brownish olive.

N=N -CH=N CH;

37 OH HO .-.do Olive.

OH=N N 0,

N H-CO CH;

38 OH HO d0 D0.

OH==N N O 7 39 OH HO N0: ..d02 Brownish olive.

CH=--N- C1 OH H0 40 d0 Olive.

-N=N -N=CH OH;

41 OH HO OzN OH NH: Greenish olive.

-o N=N N=CH N=N- S0 NH:

42 N 0: N H, D0.

-N=N OH HO S0, 0H

-0 CH; :01! N=N OzN N H:

43 Olive.

H OH HO CH=-N NO:

the dyebath; the whole is heated to boiling within minutes and kept for45 minutes at the boil. The wool is then rinsed with cold Water anddried. The olive green dyeing obtained is excellently lightfast.

Example 80 100 g. of well dampened silk are introduced at a temperatureof about 45 into a dyebath of a solution of 2 g. of the dyestuif ofExample 7 in 4000 ml. of water. 2 g. of acetic acid are added to thedyebath which is then heated within half an hour to boiling and kept atthe boil for minutes. The silk is then rinsed with Water and dried. Theolive green dyeing obtained is very lightfast.

Example 81 100 g. of polyamide fabric are introduced at a temperature of40-50" into a dyebath which has been prepared by dissolving 2 g. of thedyestuff of Example 45 in 4000 ml. of Water and adding 2 g. of the typeof auxiliary which is the condensation product of a fatty alcohol (C Cwith (15-20 molecular equivalents of) ethyl oxide, as well as 2 g. ofammonium sulfate. The dyebath is heated within half an hour to boilingand kept for one hour at the boil. The fabric is then rinsed with waterand dried. The olive green dyeing obtained is excellently lightfast.

TABLEContinucd I II III IV Shade of the N0. Azo-azorncthlnc dyestufi Azodyestutr 2:1 Chromium complex compound on wool N O: IIIHH 76 OH HO OHOlive.

SO2 -OH:N N=N OzN- -NH2 I|\TI-IC 0 CH:

77 -OH Same as No. 70 Do.

-N=N -0H=N NO2 Example 78 We claim:

1. A dyestuff of the formula 2 g. of the dyestutf according to Example 4are r solved in 4000 ml. of water and 100 g. of previously well F wettedwool are introduced into the dyebath at 40-50". x 2 g. of 40% aceticacid are then added to the bath where- 1 N c5 n upon it is brought tothe boil within half an hour and kept i at the boil for 45 minutes. Thewool is then rinsed with 40 0 0 1 cold water and dried. The green wooldyeing has excellent fastness to light. cr- Example 79 ---.Z

0 2 100 g. of well dampened wool are introduced at a N a temperature ofabout 45 into a dyebath consisting of a 45 solution of 2 g. of thedyestuff of Example 2 in 4000 ml. Y N N E of water. 3 g. of ammoniumsulfate are then added to wherein D represents phenyl or linked inOC-pDSitiOn to -CH=, and in fl-position to the R represents hydrogen,lower alkyl, hydroxy-lower alkyl or phenyl, one of X and X representsthe grouping GN=N- and-the other X represents G'N=N- or hydrogen, nitro,halogen, phenylsulfonyl or lower alkanoylarnino,

G represents phenyl, halogen-substituted phenyl, lower alkyl-substitutedphenyl, nitrophenyl, lower alkoxyphenyl, phenoxyphenyl, loweralkylphenoxyphenyl, halogen substituted phenoxyphenyl, phenylsulfonylphenyl, lower alkyl-substituted phenyl-sulfonyl-phenyl orhalogen-substituted phenyl-sulphonyl-phenyl, naphthyl or2-benzothiazolyl,

Y represents hydrogen, nitro, halogen or lower alkyl,

Y represents hydrogen or halogen,

Z represents sulfo, carboxyl, sulfamyl, lower alkyl-sulfonyl or N-loweralkyl-substituted sulfarnyl, and

Z represents hydrogen or sulfamyl, lower alkylsulfamyl or N-loweralkyl-substituted sulfamyl,

each of Z and Z being linked to an aromatic ring carbon atom of A, B, C,D, E or G.

2. A dyestutf of the formula wherein one of X and X represents thegrouping G'N==N- and the other X represents G'-N=N or hydrogen, nitro,halogen, phenylsulfonyl or lower alkanoylamino,

G represents phenyl, halogen-substituted phenyl, lower alkyl-substitutedphenyl, nitrophenyl, lower alkoxyphenyl, phenoxyphenyl, loweralkylphenoxyphenyl, halogen-substituted phenoxyphenyl, phenyl-sulfonyhphenyl, lower alkyl-substituted phenyl-sulfonyl-phenyl r formula:

=N: :ro

26 4. A dyestutf which in its free acid form is of the formula:

x-K N0 0 O N0 Cr\ i 0/ NH on sort 2 SN 3 5. A dyestutf which in its freeacid form is of the formula:

CH=N

n N no 0 l 2 o o NO 61 6. A dyestutf which in its free acid form is ofthe formula:

7. A dyestutf which in its free acid form is of the formula:

27 8. A dyestuff which in its free acid form is of the formula:

CH N

0 ozNs N N 9. A dyestuff which in its free acid form is of the formula:

SO H

28 10. A dyestufi of the formula:

References Cited UNITED STATES PATENTS 2,985,646 5/1961 Schetty et al.260

FOREIGN PATENTS 565,697 9/ 1958 Belgium.

OTHER REFERENCES Stright et al., Dyestufis, vol. 44, N0. 8, June 1963,pp. 252 8.

CHARLES B. PARKER, Primary Examiner.

D. TA'PUG A, Assistant Examiner.

